1. Field of the Invention
The present invention relates to an oxide superconducting wire and method of producing the same. More particularly, the invention relates to oxide superconducting wires and methods of producing the same that are intended for applications in such fields as electric power supply, transportation, high-energy physics, and medical instruments.
2. Description of the Background Art
In recent years, it has been reported that sintered oxide materials exhibit superconducting property at high critical temperatures, and practical applications of superconduction technology are being promoted by utilizing such superconductors. It has also been reported that an yttrium-based oxide brings about superconducting property at the temperature of 90 K and a bismuth-based oxide at the temperature of 110 K. These oxide superconductors are hopefully expected to serve practical use, because they exhibit superconducting property in liquid nitrogen, which can be available at relatively low cost.
In order to use such a superconductor to carry AC current for electric power supply, for example, the superconductor is formed into a superconducting wire or strand, in which it is covered with a silver sheath that is coated with a high-resistance material having a metal coating thereon.
Superconducting wires having such structures as described above are disclosed in International Publication No. WO96-28853, and Japanese Patent Application Laid-open Gazette Nos. 11-7846 (Patent Gazette No. 2992502), 10-50152, 10-247428, 3-15116, 11-312420, 3-15115, and 1-140520 (Patent Gazette No. 2877149).
International Publication No. WO96-28853 discloses a structure of an oxide superconducting wire, wherein each of the oxide superconductors is individually surrounded by, for example, a silver sheath that is surrounded by a metal casing, which is oxidized to form a high-resistance layer between the silver and the casing.
Japanese Patent Application Laid-open Gazette No. 11-7846 discloses a structure of an oxide high-temperature superconducting wire comprising superconducting ceramic filaments each of which is surrounded by a first layer of silver alloy that is covered with an oxygen-permeable non-superconducting ceramic layer that is surrounded by a second layer of silver alloy.
Japanese Patent Application Laid-open Gazette No. 10-50152 discloses a structure of an oxide superconducting wire comprising oxide superconducting filaments each of which is surrounded by a silver sheath that is covered with a resistive alloy (a high-resistance material) that is oxidized to form an insulating oxide between the silver sheath and the high resistive alloy.
Japanese Patent Application Laid-open Gazette No. 10-247428 discloses a structure of a multifilament oxide superconducting wire comprising a plurality of oxide superconducting strands that are individually covered with metal layers in which the resistivity of the outer metal layer is higher than that of the inner metal layer.
Japanese Patent Application Laid-open Gazette No. 3-15116 discloses an oxide superconducting wire having anisotropy. The wire comprises a core and a superconducting layer thereon. The superconducting layer surrounds the core in such a configuration that a specific crystallographic axis of the layer is oriented toward the core. The superconducting layer is divided into a plurality of segments and provided in configurations elongated in the circumferential direction as compared with the radial directions. This publication also discloses another oxide superconducting wire, wherein a high-resistance layer consisting of a resistive material is placed between a plurality of superconducting layers.
Japanese Patent Application Laid-open Gazette No. 11-312420 discloses an oxide superconducting wire comprising a plurality of oxide superconductors, each surrounded by a silver-based sheath that is surrounded by a high-resistance layer formed of a material including a heat-resistant ceramic, and further comprising an overall coating made of a material inert to the material of the high-resistance layer in a hot oxidizing atmosphere.
Japanese Patent Application Laid-open Gazette No. 3-15115 discloses a metal-coated oxide superconducting wire in which an oxidation-resistant metal is used as a cladding.
Japanese Patent Application Laid-open Gazette No. 1-140520 discloses a technology for subjecting a metal pipe, which is filled with a ceramic powder, first to plastic deformation to reduce its cross sectional area and thereafter to a heat treatment. This application also discloses a method of subjecting a metal pipe to hot plastic deformation so as to produce a small-diameter oxide superconducting wire having sufficient strength and toughness as well as high critical current density and high critical temperature.
The aforementioned oxide superconducting wires, however, have the following disadvantages.
A multifilament oxide superconducting wire incorporating silver sheaths is disadvantageous in that AC loss cannot be reduced sufficiently because silver as a sheath has low resistance. In the techniques disclosed in the aforementioned publications, superconducting filaments (covered by silver) are enclosed by barriers consisted of such as metal oxide having the insulating or resistive property for the purpose of the reduction of AC loss. However, it is difficult to make such barriers with a uniform density and thickness in limited spaces between the filaments. This subsequently makes it difficult to increase perpendicular resistance between the filaments to such a desirable level as to reduce AC loss. Furthermore, making the barrier layers thicker to realize sufficient resistance may, in turn, lead to decreasing the ratio of the superconducting filaments contained in the total oxide superconducting wire and subsequently making current density lower.
Conventionally, barriers of a high-resistance material consisting of, for example, a metal oxide are formed by coating a slurry containing a metal oxide on the outer surface of the silver sheath covering the filaments. Upon coating the slurry, the barrier layers tended to have such a low density that they were prone to irregular deformation and were not formed uniformly.
Furthermore, Japanese Patent Application Laid-open Gazette No. 63-239741 discloses a method of producing a superconducting wire. In the method, a slurry of an oxide-based superconductor and a slurry of a non-superconducting inorganic material are disposed such that the former is surrounded by the latter, and they are extruded through a die by either pressing or taking advantage of the weight of the slurries to produce a composite wire. After the composite wire is heated for drying and reduced its cross-section, the composite wire is covered with a metal tape, while being twisted at the same time.
The superconducting wire produced by the aforementioned method, however, can be neither drawn nor rolled any more, as it is covered with a metal tape. This prevents the crystallic axis of the oxide superconductors from being oriented uniformly, lowers critical current, and consequently makes it difficult to apply the superconducting wire to a practical use.
Further the conventional oxide superconductors were not capable of effectively releasing oxygen and other gases outside that were generated during a reaction process, as the superconductors were coated with silver sheaths. Consequently, as the reaction progressed to some extent, the internal pressure in the filaments increased to cause the crystal grains to be pushed apart, thereby creating interstices within the filaments. Japanese Patent Application Laid-open Gazette No.3-138820 discloses a method of producing an oxide superconductor that has a high critical current density. According to the method, the precursor of oxide superconductor is subjected to a second-stage plastic deformation to eliminate such interstices and increase its density, and then to a second-stage heat treatment. It is impossible, however, to completely bond the plural crystal grains of the oxide superconductor together, once they are formed as a result of the reaction, even if such subsequent second-stage plastic deformation and heat treatment are conducted. In heat treatment, excessively increased temperature for bonding the crystal grains may cause the once-formed oxide superconductor to melt and break up into different phases including a non-superconducting phase. A cross-section reduction ratio of plastic deformation and compressive stress applied to the oxide superconductor, if increased excessively, may create cracks of the crystal grains in the oxide superconductors and increase a portion where the bonding between the grains is not sufficient.
As described so far, the conventional methods may lower the critical current density of an oxide superconductor depending on the conditions. Even if such conditions are carefully selected to realize the highest critical current density based on the conventional methods, filaments contained in an oxide superconducting wire are aggregation of crystal grains as small as several μm, in which non-superconducting phases remain dispersed. Some crystal grains in a superconducting phase are so weakly bonded that they may show resistance in small magnetic fields and electric currents, thus lowering the critical current density.
Conventional oxide superconducting wires employed metal pipes, especially expensive silver pipes, considering their effective affinity with the oxide superconductors. For the production of multifilament superconducting wires based on conventional methods, a prolonged process is required, including steps of manufacturing both monofilament and multifilament wires. For the aforementioned reasons, overall production cost has soared and become a major impediment to wider applications of an oxide superconducting wire as an industrial product.